This invention relates to the preparation of chemically aggregated composite pigments, using organo-silicon compounds. The products are useful as fillers and in coatings for paper.
The aggregated composite mineral pigments of this invention are prepared from a starting feed mixture of a fine particle size kaolin with one or more fine particle size pigments such as a calcium carbonate and/or titanium dioxide. In our U.S. Pat. No. 5,298,066, application, it is primarily kaolin which is aggregated and such technology is broadly relevant to the present invention.
Kaolinite occurs naturally as clay, which is mined and processed to produce kaolin pigments for use in paper filling and paper coating applications. In general, the objectives of using a kaolin pigment are to improve qualities of the paper product, such as opacity, brightness, smoothness, printing, porosity, surface coverage, light scatter, and to reduce the cost of paper manufacturing. Various methods are commonly employed to enhance the performance of a given kaolin pigment. Among these are calcining and chemical aggregating methods which improve the brightness and opacity imparted to paper by a given kaolin pigment.
The brightness and opacity imparted to paper by a given kaolin (or other mineral) filler are quantitatively related to a property of the filler identified as the "scattering coefficient S." This scattering coefficient S of a given filler pigment is a property well known and extensively utilized in the paper technology art, and has been the subject of numerous technical papers. The early exposition of such measurements was made by Kubelka and Munk, and is reported in Z. Tech Physik 12:539 (1931). Further citations to the applicable measurement techniques and detailed definitions of the said scattering coefficient are set forth at numerous places in the patent and technical literature. Reference may usefully be had in this connection, e.g., to U.S. Pat. Nos. 4,026,726, and 4,028,173. In addition to the citations set forth in these patents, reference may further be had to Pulp and Paper Science Technology, Vol. 2, "Paper" Chapter 3, by H. C. Schwalbe (McGraw-Hill Book Company, N.Y.).
In a filled paper, higher light scattering allows paper to look more opaque without increasing light absorption. The use of pigment with a higher light scattering coefficient allows reduction in either the basis weight or amount of filler required to achieve targeted properties; for example, opacity and brightness. Traditionally, this has been achieved using titanium dioxide, calcined clays and precipitated calcium carbonate. The relatively higher light scattering of titanium dioxide is due to higher refractive index. Higher light scatter observed with calcined kaolin and precipitated calcium carbonate is believed to be due to the intrinsic porous structure developed during the process of manufacturing of these pigments. See McConnell et al., U.S. Pat. No. 4,381,948.
In general, the attempt to increase light scatter by modification of the kaolinite mineral also induces some increase in pore void volume. In addition, such modification can produce pigments with particle size distribution in a fairly narrow range. For example, calcining of fine kaolinite above its dehydroxylation point can produce a product with increased pore void volume. In U.S. Pat. No. 4,826,536, issued May 2, 1989, to Raythatha et al., similar aggregation is achieved chemically by reacting fine kaolinite clay with rapidly hydrolyzing metal chlorides. The acidic byproduct of this reaction may be neutralized with gaseous ammonia. In Raythatha et al., U.S. Pat. No. 4,818,294, and in Brown et al., U.S. Pat. No. 4,935,062, similar aggregates may be produced by reaction with organo-silicon compounds that are non-corrosive and produce no solid byproducts. The light scattering coefficient and pore void volumes of these clays are significantly higher than the starting kaolinite material.
Marginal increase in light scatter (generally less than 10 units) may be induced by mixing kaolinite particles of different size or by chemical flocculation. However, these structures are generally unstable and would break down under the high shear stress of paper making or paper coating.
Aside from use as fillers, the aggregated pigments are used in paper coating to improve surface coverage. The application of such pigments can lead to a smoother surface, higher porosity, gloss and print properties. In Raythatha U.S. Pat. No. 4,818,294, a chemically aggregated kaolin pigment is shown to significantly increase coated sheet properties, especially paper and print gloss.
In more detail, in U.S. Pat. No. 4,381,948, to McConnell et al., a calcined kaolin pigment and a method for manufacture of same are disclosed. The said pigment consists of porous aggregates of kaolin platelets, and exhibits exceptionally high light scattering characteristics when incorporated as a filler in paper. This pigment, which substantially corresponds to the commercially available product ALPHATEX.RTM. of the present assignee, ECC International Inc. (Atlanta, Ga.), is prepared by first blunging and dispersing an appropriate crude kaolin to form an aqueous dispersion of same. The blunged and dispersed aqueous slurry is subjected to a particle size separation from which there is recovered a slurry of the clay, which includes a very fine particle size; e.g. substantially all particles can be smaller than 1 micrometer E.S.D. The slurry is dried to produce a relatively moisture-free clay, which is then thoroughly pulverized to break up agglomerates. This material is then used as a feed to a calciner; such feed is calcined under carefully controlled conditions to typical temperatures of at least 900.degree. C. The resulting product is cooled and pulverized to provide a pigment of the porous high light scattering aggregates of kaolin platelets as described.
Calcined kaolin products, including those of the aforementioned ALPHATEX.RTM. type, are seen to be manufactured by relatively complex techniques involving a multiplicity of steps, including specifically a calcining step, plus various preparatory steps and post-calcining steps. Thus, the said product is relatively expensive to produce, and requires considerable investment in complex apparatus and the like; e.g. highly regulated calciners, etc. The particle size in the feed to the calciner must be carefully controlled, because a relatively small increase in coarseness of such feed can have very marked detrimental effect on Valley abrasion. Furthermore, calcination per se will produce an abrasive product if overheating occurs. Consequently, the conditions of preparation of calcined materials must be very carefully controlled in order to keep abrasion acceptably low in the calcined product.
In Raythatha U.S. Pat. No. 4,826,536, a process is disclosed in which a fine particle size kaolin is reacted in particulate form with a metal chloride, such as silicon tetrachloride, to form a chemically aggregated structured kaolin pigment. The metal chloride may be one or more of the chlorides having the general formula MCl.sub.x, where M is Si, Ti or Al; and X is 3 or 4 depending on the valence of M. Heating may optionally be used to shorten the reaction time. When so used, temperatures generally will not, however, exceed about 150.degree. C. In order to complete the polymerization and condensation which is thought to occur, it is preferable to age the resulting product for a period, typically at least three days. In another aspect of that process, additional improvements in the products are found to occur by the addition of ammonia to the combined kaolin and metal chloride.
Thus Raythatha U.S. Pat. No. 4,826,536, describes methods of preparing chemically aggregated kaolinite pigment using very reactive metal chlorides such as silicon tetrachloride and titanium tetrachloride. The application of such reactive metal chloride leads to aggregated products that give enhanced optical and printability properties for filled and coated papers. However, due to the nature of the aggregating chemical, very specialized equipment and processing steps are required. In addition, the resultant by-products are difficult to remove by ordinary methods. Furthermore, the aggregated kaolinite pigment product cannot be dispersed effectively in water at solids contents above 50 weight percent, which is an impediment to their shipping and use.
In Raythatha U.S. Pat. No. 4,826,536, free moisture present in the particulate feed is useful to initiate at least a partial hydrolysis of the metal chloride or chlorides. The patentee indicates that if the moisture level is too high, however, it can diminish or impair the efficiency of the aggregation process. Thus in the instances where silicon and/or titanium chlorides are used, if the moisture level is too high relative to the metal chloride(s), then the hydrolysis products from the metal chlorides will predominantly precipitate as the metal oxide, i.e. as silica gel and/or titania. In the case of aluminum trichloride, if the moisture level is too high relative to the metal chloride, then the dilution of the finally resulting aluminum hydroxide (in the presence of ammonia) can be so high as to cause inefficient aggregation.
Raythatha U.S. Pat. No. 4,818,294, discloses a method of producing aggregated kaolin pigments using organo-silicon compounds either singly or in combination. In general, the compounds may be selected from symmetric compounds having the formula ##STR1## where R.dbd.CH.sub.3, C.sub.2 H.sub.5, C.sub.3 H.sub.7, N--C.sub.4 H.sub.9 sec-C.sub.4 H.sub.9 and C.sub.6 H.sub.5 and asymmetric compounds having the formula ##STR2## where R.dbd.C.sub.2 H.sub.5, X.dbd.Cl or Br, and R'.dbd.H.
In a typical process, substantially dry kaolin mineral is treated with an effective amount of an organo-silicon compound such as silanes having the formula (RO).sub.4 Si, where R is a lower alkyl group of 1 to 4 carbon atoms; e.g., methyl (CH.sub.3) or ethyl (CH.sub.3 CH.sub.2). The R groups in the silane can be the same or different. The resulting products exhibit increased light scatter, improved wet void volume and bulk, and have a structure that is strong enough to withstand the high shear forces of paper making and paper coating. The amount of organic silicon compound may range from 0.1 to 3.0%, preferably from 0.2 to 2.0% by weight of dry kaolin.
Raythatha U.S. Pat. No. 4,818,294, also teaches that aggregation enhancing chemicals, comprising alkaline earth metal salts and lithium chloride, may optionally be used, in amounts in the range of 0.05 to 3.0%, typically 0.05 to 2% by weight of the salt based on the weight of the dry kaolin.
Raythatha U.S. Pat. No. 4,818,294, further teaches that feed moisture is typically in the range of 1 to 2%, preferably 1.0 to 1.75%, by weight of the feed clay. The most preferred range is 1.5 to 1.75% by weight of the clay. Brown No. 4,935,062, a continuation-in-part of Raythatha U.S. Pat. No. 4,818,294, discloses that the organo-silicon compounds of Raythatha U.S. Pat. No. 4,818,294, are useful for producing aggregated kaolin pigments by the method of the Raythatha U.S. Pat. No. 4,818,294, patent when the moisture content of the feed is increased into the range of 2.0 to 5.0% by weight of the clay. Brown further teaches that moisture content above 5% causes the clay to become sticky and difficult to handle.
Thus Raythatha U.S. Pat. No. 4,826,536, Raythatha U.S. Pat. No. 4,818,294, and Brown U.S. Pat. No. 4,935,062, all disclose and teach that aggregated kaolin pigments can be produced by treating a kaolin clay with organo-silane or metal chloride compounds in the presence of a quantity of water that is sufficient to hydrolyze and polymerize the organo-silane or metal chloride compounds, i.e. up to about 5% of the weight of clay. These patents teach that it is necessary to restrict the amount of moisture used, and Raythatha U.S. Pat. No. 4,826,536, teaches that when higher amounts of moisture are present the hydrolysis products formed are ineffective for producing aggregated pigment.
Using the prior art of Brown U.S. Pat. No. 4,935,062, one would process the crude clay to a dried product, and then mix in the selected organo-silane to produce an aggregated product. In practice this procedure has been found to require an aging period of at least three days from the time the clay is treated until it can be used--e.g. in paper coating. This has resulted in severe impediments to ease of production and use of the pigments.
Additional prior art pertinent to the present invention includes:
U.S. Pat. No. 3,567,680, issued to Joseph Iannicelli disclosing that mercaptopropyl silanes having the formula: ##STR3## wherein Z is selected from the group consisting of hydrogen, cation, alkyl, aryl, alkylaryl, arylalkyl and derivatives thereof; X is selected from the group consisting of alkyl, alkylaryl, and arylalkyl; and R1, R2 and R3 are selected from the group consisting of hydrogen, cation and alkyl, are suitable for modifying kaolin clays to enable them to be used as reinforcing fillers for elastomers. It may be noted that in Iannicelli, only the trialkoxy mercaptopropyl silanes are considered. Blends of these mercapto organosilanes with amino organosilanes are also disclosed.
U.S. Pat. No. 3,364,059, to Marzocchi, discloses a method for treating glass fibers to improve their bonding relationship to rubbers by treating them with a silane containing a thio group.
In U.S. Pat. No. 3,834,924, to Thomas G. Grillo, an amino organosilane is added to a high solids content pigment dispersion or slurry to change the slurry form into a thick, flocculated and plastic type that is suitable for extrusion and drying. Because a thick, cake-like product is formed, the amino organosilane and pigment dispersion are preferably mixed or blended directly in a solids mixing apparatus such as an extruder, designed to extrude the plastic mass in the form of a compacted rod type body which may be fed directly into a drier. The products are useful as a filler for polyurethanes. As can be seen, the described treatment is for the different purpose of forming a flocculated, plastic mass of the kaolin, not for the purpose of aggregating fine kaolin particles to form aggregated fine kaolin particles.
In U.S. Pat. No. 3,894,882, to Robert B. Takewell et al., a rotating pelletizing drum is used to form pellets from clay such as kaolin clay. To avoid the problem of dust, a wetting liquid is introduced into the drum, preferably steam or steam/water. The steam adds heat to the pellets to aid in drying them. There is an incidental mention of using "other suitable wetting liquids", an extensive list being given which includes silanes.
In accordance with the foregoing, an object of the present invention is to provide an improved process for producing an aggregated composite pigment product which possesses improved pigment bulk, porosity and light scattering characteristics, and hence is useful as a bulking pigment for coating of paper and paper board, and which may also be used as an opacifier and light scattering filler for paper and paper board as well as in other paper manufacturing applications.
A further object of this invention is to provide a method for producing a chemically aggregated composite pigment by means of a process which permits handling and treatment of the feed in a substantially dry state, and which yet produces aggregates having sufficient strength to enable their effective use in coating applications.